CN111068712A - Bifunctional catalyst for simultaneously removing oxygen and nitrogen oxide, preparation method and application thereof - Google Patents
Bifunctional catalyst for simultaneously removing oxygen and nitrogen oxide, preparation method and application thereof Download PDFInfo
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- CN111068712A CN111068712A CN201811223052.XA CN201811223052A CN111068712A CN 111068712 A CN111068712 A CN 111068712A CN 201811223052 A CN201811223052 A CN 201811223052A CN 111068712 A CN111068712 A CN 111068712A
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- catalyst
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- nitrogen oxides
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000001301 oxygen Substances 0.000 title claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 45
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 30
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 10
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 4
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 45
- 150000001336 alkenes Chemical class 0.000 abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 52
- 238000005470 impregnation Methods 0.000 description 50
- 239000000243 solution Substances 0.000 description 32
- 239000010949 copper Substances 0.000 description 19
- 239000007788 liquid Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- -1 Co and the like Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100001143 noxa Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910006415 θ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalysts for simultaneously removing oxygen and nitrogen oxides, and discloses a bifunctional catalyst for simultaneously removing oxygen and nitrogen oxides, a preparation method thereof, and a method for simultaneously removing oxygen and nitrogen oxides from a feed gas. The catalyst comprises an active component and a carrier, wherein the active component comprises a main catalytic active component and an auxiliary catalytic active component, the main catalytic active component is Pd, the auxiliary catalytic active component is selected from one or more of Cu, Mn, Fe, Co and Zn, and the content of the auxiliary catalytic active component is 2-10 wt% based on the total weight of the catalyst. The catalyst of the invention can remove oxygen and nitrogen oxide at lower temperature, has good removal performance and good selectivity, and can effectively reduce the generation of side reaction of olefin hydrogenation.
Description
Technical Field
The invention relates to the field of catalysts for simultaneously removing oxygen and nitrogen oxides, in particular to a bifunctional catalyst for simultaneously removing oxygen and nitrogen oxides, and a preparation method and application thereof.
Background
Generally, some production processes in the industries of petrochemical industry and the like need to perform deoxidation treatment on gas materials in order to make the oxygen content in the system reach a trace amount due to safety considerations. The refinery catalytic cracking dry gas contains CO and CO2、NH3、NOXAs, Hg, As and other harmful impurities, 0.01-0.1% of O2. These impurities have a great influence on the recycling of the dry gas. In the ethylene low-temperature rectifying device, the strict requirement on the content of the components of the concentrated ethylene-rich dry gas is met, namely O2Less than or equal to 1 ppm. The concentrated ethylene-rich dry gas must be deeply purified to remove trace oxygen, nitrogen oxides and other impurities. Therefore, the removal and purification of oxygen and nitrogen oxides in the gas have important significance in the industries of chemical engineering, environmental protection and the like.
On the other hand, with the development of modern industries in various countries around the world, air pollution has become an increasingly serious global problem. The nitrogen oxide is one of main pollutants in the atmosphere, forms acid rain, brings potential safety hazards to petrochemical production, and has explosion danger when being enriched in a low-temperature cold box. O contained in catalytic dry gas2With NOXReaction at low temperature to form N2O3And N2O4And with NH3The reaction produces solid ammonium nitrate and ammonium nitrite, which are extremely unstable and subject to heat or shock, all of which present a risk of explosion.
Nitrogen oxidesThe catalytic reduction removal of (1) is a hotspot of recent research, a catalyst carrier comprises alumina, a molecular sieve and the like, active components comprise Pt, Pd, Ag, Cu, W, Ni, Co and the like, and a reducing agent comprises H2、CH4、C3H6CO and alcohols, etc. and the catalyst and its eliminating process are used mainly in treating automobile tail gas, FCC regeneration, refinery exhaust and other environment.
The catalytic deoxidation is to make O in the gas under the action of a catalyst2And H2And CO and other components with reducing performance react to be removed. The existing deoxidation catalyst can be roughly divided into a noble metal catalyst and a non-noble metal catalyst, the noble metal catalyst is mainly a palladium catalyst and is expensive, active components of the non-noble metal catalyst are molybdenum, cobalt, nickel, tungsten and the like, the active metal components exist in an oxidation state, and the active metal components need to be vulcanized to have good hydrodeoxygenation activity, selectivity and stability after being converted from the oxidation state to the vulcanization state.
The catalytic deoxidation is to make O in the gas under the action of a catalyst2And H2And CO and other components with reducing performance react to be removed. As disclosed in CN1087655C and CN1030895C, noble metals such as Pt and Pd are mostly used as active components, and such catalysts have high activity and can be used at room temperature, but such catalysts have strict requirements on raw materials and cannot contain impurities such as sulfide that poison the catalysts.
CN101165030B discloses a Mn-Ag dual-active component deoxidizer, which is used for removing trace oxygen in ethylene and propylene, can remove oxygen to below 0.05ppm at room temperature, but the deoxidizer catalyst can ensure stable deoxidizing activity only by repeated reduction and regeneration in the using process, has lower treatment capacity per unit time, and can increase the cost when being used in the polyolefin industry.
CN1413765A discloses a catalyst for ammonia selective reduction of nitrogen oxides, which is a copper and manganese composite oxide catalyst loaded on alumina, and has high activity and stability under the conditions that the reaction temperature is 150-350 ℃.
CN106423143A discloses a method for preparing nitrogen oxideThe catalyst for low-temp. selective catalytic reduction removal technology uses anatase titanium dioxide with specific preferential exposed surface (001) as carrier and adopts impregnation method to prepare supported type V2O5-WO3/TiO2A catalyst. The catalyst has good denitration activity, NO conversion rate and N generation in a medium-low temperature section (200-2The selectivity of (A) is over 90 percent.
In the field of petrochemical engineering, for NO in FCC processesXAre more studied, e.g. US5340554A discloses the use of hydrogenation catalysts for the removal of NO from refinery gasesXThe method takes Co-No-Si or Fe-Cr as active components to prepare the catalyst, and NO in the hydrocarbon-containing refinery gas are removed under the conditions of reaction temperature of 150 ℃ and 190 ℃ and pressure of 0.8-1.1MPa2，NOXThe average removal rate of (A) is less than 50%.
CN101391224A discloses a catalyst for removing oxygen and nitrogen oxides from hydrocarbon-containing gas and a removing method thereof, wherein a catalyst carrier is modified gamma-alumina, and active components comprise: (1) at least one selected from Mo, W and Cr; (2) at least one of Ni and Co; (3) p or citric acid; (4) and (3) an auxiliary agent Ce. When the obtained catalyst is applied to removing oxygen and nitrogen oxides from hydrocarbon-containing gas, the performance of the catalyst for removing oxygen and nitrogen oxides is good under the conditions of the catalyst sulfuration state and the reaction temperature of 120-260 ℃. And when sulfur is not present, the activity and stability of the catalyst are poor.
Some of the catalysts can not simultaneously remove oxygen and nitrogen oxides, some catalysts can ensure better catalytic activity and stability only in a sulfidation state, and some catalysts can generate a catalyst poisoning phenomenon in the presence of sulfides.
Therefore, there is a need for a catalyst that can be easily used to remove both oxygen and nitrogen oxides.
Disclosure of Invention
The invention aims to solve the problems that the prior art catalyst needs to be vulcanized before use, cannot simultaneously remove oxygen and nitrogen oxides and the like, and provides a bifunctional catalyst for simultaneously removing oxygen and nitrogen oxides, and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a bifunctional catalyst for simultaneously removing oxygen and nitrogen oxides, the catalyst comprising an active component and a carrier, wherein the active component comprises a main catalytic active component and a promoter active component, the main catalytic active component is Pd, and the promoter active component is selected from one or more of Cu, Mn, Fe, Co and Zn; wherein, the content of the catalytic promoting active component is 2-10 wt% based on the total weight of the catalyst.
In a second aspect, the present invention provides a process for preparing a catalyst according to the first aspect of the present invention, which comprises:
(1) selecting a catalyst carrier;
(2) and loading a Pd source and a promoter active component precursor on the catalyst carrier, drying and roasting.
In a third aspect, the invention provides the use of a catalyst according to the first aspect of the invention for the simultaneous removal of oxygen and nitrogen oxides.
The catalyst can remove oxygen and nitrogen oxides in raw material gas at the same time at a lower temperature, does not need to be vulcanized before use, does not need a hydrogen sulfide environment in the application process, has good removal performance and good selectivity, and can effectively reduce the generation of side reactions of olefin hydrogenation. When the catalyst is used for simultaneously removing oxygen and nitrogen oxides in raw material gas, the oxygen in the raw material gas can be removed to be below 1ppmv, and the nitrogen oxides can be removed to be less than 10 ppbv.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a bifunctional catalyst for simultaneously removing oxygen and nitrogen oxides, which comprises an active component and a carrier, wherein the active component comprises a main catalytic active component and a cocatalyst active component, the main catalytic active component is Pd, and the cocatalyst active component is selected from one or more of Cu, Mn, Fe, Co and Zn; wherein, the content of the catalytic promoting active component is 2-10 wt% based on the total weight of the catalyst.
In the catalyst of the present invention, the content of the co-catalytic active component is 2 to 10 wt%, for example, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt% and any value in the range formed by any two of these points, preferably, the content of the co-catalytic active component is 4 to 8 wt%, based on the total weight of the catalyst; the content of Pd is 0.01 to 0.3 wt%, and for example, may be 0.05 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, or any value in a range of any two of these, preferably, the content of Pd is 0.1 to 0.3 wt%, and more preferably, the content of Pd is 0.05 to 0.2 wt%.
In the present invention, the above-mentioned content is understood as a content in terms of metal elements.
In order to better achieve the simultaneous removal of oxygen and nitrogen oxides, the weight ratio of Pd to the promoter active component is 1: (6-1000), preferably 1: (10-200).
In a preferred embodiment, the active components of the catalyst comprise: 0.01-0.3 wt% Pd; 2-10 wt% Cu.
In the catalyst, Pd is in the form of metal simple substance and/or metal oxide, and the catalytic promoting active component such as at least one of Cu, Mn, Fe, Co and Zn is in the form of metal simple substance and/or metal oxide; preferably both Pd and the co-promoter active component are present in the form of elemental metal.
In the present invention, the carrier is selected from one or more of aluminum trioxide, activated carbon, silica and molecular sieves, preferably the carrier is aluminum trioxide, more preferably alumina trihydrate. The aluminum trioxide carrier can be gamma-Al2O3、δ-Al2O3、θ-Al2O3、α-Al2O3Etc., preferably gamma-Al2O3And α -Al2O3The shape can be spherical, strip, clover, column, etc., and is preferably spherical carrier.
The catalyst can be used for simultaneously removing oxygen and nitrogen oxides from raw material gas, wherein the raw material gas can be hydrocarbon-containing gas or mixed gas containing inert gases such as nitrogen and the like. The hydrocarbon-containing gas may contain 1 to 99.9% of hydrocarbon compounds, and the balance may be N2、CO、CO2And H2And the like. In one embodiment, the hydrocarbon-containing gas may have an olefin content of 2 to 90%.
The inventor finds that the matching of the main catalytic active component Pd and the cocatalyst active component can realize synergistic effect, so as to realize the effective removal of oxygen and nitrogen oxide from the raw material gas at the same time, and furthermore, when the weight ratio of the main catalytic active component Pd to the cocatalyst active component is 1: 10-200) to further improve the removal effect of oxygen and nitrogen oxides, and remove the oxygen in the feed gas to a content of less than 1ppmv and the nitrogen oxides in the feed gas to a content of less than 10 ppbv. In the present invention ppmv means 1/106Volume ratio, ppbv means 1/109Volume ratio.
In a second aspect, the present invention provides a process for preparing a catalyst according to the first aspect of the present invention, which comprises:
(1) selecting a catalyst carrier;
(2) and loading a Pd source and a promoter active component precursor on the catalyst carrier, drying and roasting.
In the present invention, the Pd source may be any Pd-containing compound, for example selected from soluble Pd salts, such as nitrate, acetate and/or chloride of Pd; the promoter active component precursor may be any compound containing a promoter active component, for example, selected from soluble salts of the promoter active component, such as at least one selected from nitrates, chlorides and sulfates of Cu, Mn, Fe, Co, Zn.
In the preparation method of the catalyst, a Pd source is prepared into a first impregnation liquid, a promoter active component precursor is prepared into a second impregnation liquid, and then the first impregnation liquid and the second impregnation liquid are loaded on the catalyst carrier. In the supporting process, the first impregnation liquid may be supported first and then the second impregnation liquid may be supported, the second impregnation liquid may be supported first and then the first impregnation liquid may be supported, or the first impregnation liquid and the second impregnation liquid may be supported on the carrier together. In one embodiment, the Pd source and the promoter active component precursor may be formulated into a mixed impregnation solution, and the mixed impregnation solution is supported on the carrier. The technical means of supporting the impregnation solution on the support can be chosen according to the state of the art, for example by impregnation or spraying.
In one embodiment of the method of the present invention, the Pd source is formulated into a first impregnation solution, the concentration of Pd in the first impregnation solution can be selected according to the loading amount of Pd, for example, the concentration of Pd in the first impregnation solution can be 1-20mg/ml, and the concentration of the co-catalytic active component in the second impregnation solution can also be selected according to the required loading amount, for example, the concentration of the co-catalytic active component in the second impregnation solution can be 10-500 mg/ml.
In one embodiment of the method of the invention, the Pd source and the promoter active component precursor are prepared into a mixed impregnation liquid, and the concentration of Pd in the mixed impregnation liquid can be 1-20mg/ml, and the concentration of the promoter active component can be 10-500 mg/ml.
In one embodiment of the method of the present invention, the impregnation solution is supported on the carrier using an impregnation method, and preferably, the Pd source and the promoter active component precursor are supported on the carrier using an equal volume impregnation method.
In the process of the present invention, the particle size of the carrier may be 1 to 10mm, preferably 1 to 5 mm.
In the method, a Pd source and a promoter active component precursor are prepared into impregnation liquid, and after the impregnation liquid is loaded on the catalyst carrier by adopting an equal-volume impregnation method, the carrier loaded with the active component is dried and roasted, wherein the drying conditions comprise that: the temperature is 70-130 ℃ and the time is 2-6 hours, preferably, the drying is divided into two steps: (1) drying at 70-80 deg.C for 1-3 hr, and (2) drying at 110-130 deg.C for 1-5 hr. The roasting conditions comprise: the temperature is 500-800 ℃ and the time is 2-6 hours, preferably, the temperature is 500-700 ℃ and the time is 3-5 hours.
The method of the invention also comprises a step of reducing the product obtained by sintering, and specifically the reduction can be carried out in the presence of a pure hydrogen atmosphere or a hydrogen-containing gas, and the reducing conditions comprise: the temperature is 200-400 ℃.
The catalyst of the invention can be prepared by carrying out the reduction step together with the preparation process, or can be subjected to the reduction step before being used for catalytic reaction.
In a third aspect, the invention provides the use of a catalyst according to the first aspect of the invention for the simultaneous removal of oxygen and nitrogen oxides.
In such an application, a feed gas is contacted with a catalyst according to the first aspect of the invention and a reducing gas (e.g. H) is passed over2、NH3Etc.), the volume space velocity of the raw material gas is 1000-10000h-1The reaction is carried out at a reaction temperature of 100 ℃ and 300 ℃ and a reaction pressure of 0.5-3MPa, preferably at a reaction temperature of 100 ℃ and 200 ℃ and a reaction pressure of 1-2MPa while removing oxygen and nitrogen oxides.
The catalyst of the invention can be directly used without sulfuration before and during use. The catalyst of the invention can be used for simultaneously removing oxygen and nitrogen oxides in hydrocarbon-containing gas, and the hydrocarbon-containing gas can be C-containing gas1-C20And/or an alkane, alkene and/or alkyne. The catalyst of the invention can remove oxygen and nitrogen oxides efficiently at a lower reaction temperature (such as 60-200 ℃), so that oxygen in feed gas is removed from 1000ppmvTo less than 1ppmv while removing nitrogen oxides from below 2000ppbv to less than 10 ppbv.
The application of the bifunctional catalyst in the invention for simultaneously removing oxygen and nitrogen oxides in the feed gas has the following advantages:
(1) the bifunctional catalyst is simple to prepare, wherein the multi-component catalytic active component can be impregnated at one time, so that the catalyst is suitable for large-scale industrial production;
(2) the bifunctional catalyst can simultaneously remove oxygen and nitrogen oxides in feed gas, has good selectivity, can be used under the condition of low hydrogen content (below 1000 ppmv), and can effectively reduce the occurrence of olefin hydrogenation side reaction;
(3) the bifunctional catalyst has wide application range, is suitable for any gas containing hydrocarbon compounds, can be directly used, does not need to be vulcanized before use and in the use process, has good performance of removing oxygen and nitrogen oxides under the condition of lower reaction temperature, can remove the oxygen in a gas material from 1000ppmv to less than 1ppmv, and can also remove the nitrogen oxides in the gas material from less than 2000 ppmv to less than 10 ppmv.
The present invention will be described in detail below by way of examples.
Example 1
(1) Use of
3mm of gamma-Al2O3The ball serves as a carrier.
(2) Preparing a mixed impregnation solution: preparing a palladium chloride solution, adding copper nitrate into the palladium chloride solution, and fully dissolving to obtain a mixed impregnation solution, wherein the Pd content is 3.8mg/mL in terms of Pd, and the Cu content is 200mg/mL in terms of Cu.
(3) Preparing a catalyst: and (2) impregnating the carrier by using the mixed impregnation liquid by using an isometric impregnation method, drying at the low temperature of 80 ℃ for 2 hours, drying at the temperature of 120 ℃ for 4 hours, and roasting at the temperature of 600 ℃ for 4 hours to obtain the catalyst A1, wherein the Pd content is 0.2 weight percent and the Cu content is 8 weight percent based on the weight of the catalyst.
Comparative example 1
The catalyst was prepared as described in example 1, except that the mixed impregnation solution was formulated so that the Cu content was 25mg/mL in terms of Cu, to finally obtain catalyst D1, in which the Pd content was 0.2 wt% and the Cu content was 1 wt% based on the weight of the catalyst.
Example 2
(1) Use of
3mm of gamma-Al2O3The ball serves as a carrier.
(2) Preparing a mixed impregnation solution: preparing a palladium nitrate solution, adding copper nitrate into the palladium nitrate solution, and fully dissolving to obtain a mixed impregnation solution, wherein the Pd content is 2.3mg/mL in terms of Pd, and the Cu content is 100mg/mL in terms of Cu.
(3) Preparing a catalyst: and (2) impregnating the carrier by using the mixed impregnation liquid by using an isometric impregnation method, drying at the low temperature of 80 ℃ for 2 hours, drying at the temperature of 120 ℃ for 4 hours, and roasting at the temperature of 550 ℃ for 4 hours to obtain the catalyst A2, wherein the Pd content is 0.12 wt% and the Cu content is 4 wt% based on the weight of the catalyst.
Example 3
A catalyst was prepared by the method described in reference to example 1, except that α -Al was used2O3Ball replacement of gamma-Al2O3And (4) preparing the obtained impregnation solution, wherein the Pd content is 1.5mg/mL in terms of Pd, and the Cu content is 150mg/mL in terms of Cu. Finally, catalyst A3 was obtained, in which the Pd content was 0.08% by weight and the Cu content was 6% by weight, based on the weight of the catalyst.
Example 4
The catalyst was prepared as described in example 1, except that manganese nitrate was used in place of copper nitrate to finally obtain catalyst A4 having a Pd content of 0.2 wt% and a Mn content of 8 wt% based on the weight of the catalyst.
Example 5
(1) Use of
3mm of gamma-Al2O3The ball serves as a carrier.
(2) Preparing a mixed impregnation solution: preparing a palladium nitrate solution, adding cobalt nitrate into the palladium nitrate solution, and fully dissolving to obtain a mixed impregnation solution, wherein the Pd content is 2.3mg/mL in terms of Pd, and the Co content is 200mg/mL in terms of Co.
(3) Preparing a catalyst: and (2) impregnating the carrier by using the mixed impregnation liquid by using an isometric impregnation method, drying at the low temperature of 80 ℃ for 2 hours, drying at the temperature of 120 ℃ for 4 hours, and roasting at the temperature of 650 ℃ for 3 hours to obtain the catalyst A5, wherein the Pd content is 0.12 wt% and the Co content is 8 wt% based on the weight of the catalyst.
Comparative example 2
A catalyst was prepared by referring to the method described in example 5, except that a mixed solution was prepared so that the Co content therein was 25mg/mL in terms of Co, and the rest was identical to example 5, to finally obtain catalyst D2 in which the Pd content was 0.12 wt% and the Co content was 1 wt% in terms of the weight of the catalyst.
Example 6
(1) Use of
3mm of gamma-Al2O3The ball serves as a carrier.
(2) Preparing a mixed impregnation solution: preparing a palladium nitrate solution, adding ferric chloride into the palladium nitrate solution, and fully dissolving to obtain a mixed impregnation solution, wherein the Pd content is 3.8mg/mL in terms of Pd, and the Fe content is 85mg/mL in terms of Fe.
(3) Preparing a catalyst: and (2) impregnating the carrier by using the mixed impregnation liquid by using an isometric impregnation method, drying at the low temperature of 70 ℃ for 1 hour, drying at the temperature of 110 ℃ for 4 hours, and roasting at the temperature of 700 ℃ for 3 hours to obtain the catalyst A6, wherein the Pd content is 0.05 weight percent and the Fe content is 3 weight percent based on the weight of the catalyst.
Example 7
(1) Use of
3mm of gamma-Al2O3The ball serves as a carrier.
(2) Preparing a mixed impregnation solution: preparing a palladium nitrate solution, adding zinc nitrate into the palladium nitrate solution, and fully dissolving to obtain a mixed impregnation solution, wherein the Pd content is 3.8mg/mL in terms of Pd, and the Zn content is 100mg/mL in terms of Zn.
(3) Preparing a catalyst: and (2) impregnating the carrier by using the mixed impregnation liquid by using an isometric impregnation method, drying at the low temperature of 70 ℃ for 1 hour, drying at the temperature of 130 ℃ for 4 hours, and roasting at the temperature of 750 ℃ for 3 hours to obtain the catalyst A7, wherein the Pd content is 0.15 wt% and the Zn content is 10 wt% based on the weight of the catalyst.
Oxygen and nitrogen oxide removal evaluation
The catalysts a1-a7 of examples 1-5 and the catalysts D1-D2 of comparative examples 1-2 described above were used to remove oxygen and nitrogen oxides from feed gases. The feed gas is about 95% C1-C4Refinery catalytic dry gas of hydrocarbon compounds. The catalyst is filled on a conventional small fixed bed reaction device, the filling amount is 10mL, and the catalyst is firstly subjected to pre-reduction treatment: the nitrogen containing 10 percent of hydrogen gas is used for reduction, the temperature is gradually increased to 300 ℃, the stay time is 8 hours, and then the temperature is reduced to 100-160 ℃. Introducing raw material gas into a catalyst reaction device, simultaneously adding hydrogen, and finally adding O in the raw material gas2Has a content of about 500ppmv, a NO content of about 1000ppbv, H2Content of 1000-10000ppmv, C2H4The content is 15-35 vol%. The air feeding space velocity is 3000h-1The pressure is 1.0 MPa. Reacting at the temperature of between 100 and 160 ℃ in the fixed bed reaction device, and obtaining O in a reaction outlet2And NO content are shown in table 1.
TABLE 1
As can be seen from the results in Table 1, the catalyst A1-A7 of the invention has better effects of deoxidation and denitrification oxide at lower reaction temperature, so that the outlet oxygen content is reduced to below 1ppmv, the nitrogen oxide content is reduced to below 10ppbv, the selectivity of the catalyst is better, and the occurrence of side reactions of olefin hydrogenation is reduced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A bifunctional catalyst for simultaneously removing oxygen and nitrogen oxides comprises an active component and a carrier, wherein the active component comprises a main catalytic active component and an auxiliary catalytic active component, the main catalytic active component is Pd, and the auxiliary catalytic active component is selected from one or more of Cu, Mn, Fe, Co and Zn; wherein, the content of the catalytic promoting active component is 2-10 wt% based on the total weight of the catalyst.
2. The catalyst of claim 1, wherein the Pd is present in an amount of 0.01 to 0.3 wt.%, based on the total weight of the catalyst;
preferably, the content of Pd is 0.05-0.2 wt% and the content of the co-catalytic active component is 2-10 wt%, based on the total weight of the catalyst.
3. The catalyst according to claim 1 or 2, wherein the weight ratio of the primary catalytically active component to the co-catalytically active component is 1: (6-1000), preferably 1: (10-200).
4. The catalyst according to claim 1 or 2, wherein Pd is present in the form of elemental metal and/or metal oxide and the co-catalytically active component is present in the form of elemental metal and/or metal oxide.
5. The catalyst according to any one of claims 1 to 4, the catalytically co-active component being Cu.
6. The catalyst of any one of claims 1-5, the support is selected from one or more of aluminum trioxide, activated carbon, silica, and molecular sieves; preferably, the carrier is aluminum trioxide; preferably, the carrier is γ -Al2O3And/or α -Al2O3(ii) a More preferably, the carrier is spherical gamma-Al2O3And/or spherical α -Al2O3。
7. A process for preparing a catalyst as claimed in any one of claims 1 to 6, which process comprises:
(1) selecting a catalyst carrier;
(2) and loading a Pd source and a promoter active component precursor on the catalyst carrier, drying and roasting.
8. The method of claim 7, the source of Pd is selected from nitrates, acetates and/or chlorides of Pd, and the promoted active component precursor is selected from at least one of nitrates, chlorides and sulfates of Cu, Mn, Fe, Co, Zn.
9. The method of claim 7 or 8, wherein in step (2), the drying conditions comprise: the temperature is 70-130 deg.C, and the time is 2-6 hr, preferably 80-120 deg.C, and the time is 3-5 hr;
the roasting conditions comprise: the temperature is 500-800 ℃ and the time is 2-6 hours, preferably, the temperature is 500-700 ℃ and the time is 3-5 hours.
10. Use of a catalyst according to any one of claims 1 to 6 for the simultaneous removal of oxygen and nitrogen oxides.
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Application publication date: 20200428 |
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